JPS6213187B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a method for manufacturing laminated flooring, and more specifically, it is easy to construct using ordinary adhesives, durable for practical use, and easily removable when replacing the flooring. The present invention relates to a method for manufacturing laminated flooring. (Prior art) Conventionally, the manufacturing method for this type of flooring material is to form an intermediate layer of soft plastic foam on the surface side of a core material layer made of long-fiber nonwoven fabric, and further to bond a surface layer of soft plastic film thereon. In 1977, a densely packed soft plastic layer containing a large amount of filler was bonded to the back side of the core material layer.
A method described in Publication No.-41848 is known. (Problems to be Solved by the Invention) However, in the flooring material obtained by the method described in Japanese Patent Publication No. 47-41848, the core material layer made of long fiber nonwoven fabric is used as the base material, and the surface thereof is covered with an intermediate layer of soft plastic foam. This method is characterized by bonding a dense soft plastic layer containing a large amount of filler to the back side (back side of the core material layer) of a laminate having a surface layer of soft plastic film on top of the layer. In order to first bond a dense soft plastic layer containing a large amount of filler to the back side of the core layer of the laminate, the dense soft plastic layer is bonded to the back side of the core layer. Since the fibers and nonwoven fabric are bonded only on the surface, and the two are not completely integrated, when a person walks on the flooring, they may drag heavy objects on the flooring, or they may touch the floor with a chair with casters, etc. If a load is repeatedly applied to the bonding surface, delamination may occur at the bonding surface.Secondly, when bonding a soft plastic layer with a dense structure containing a large amount of filler on the back side of the core material layer. To prevent the occurrence of wrinkles, etc.
It is necessary to apply tension to the soft plastic layer of the dense tissue, and this tension causes the soft plastic layer of the dense tissue to be bonded to the core material layer with internal strain, and due to this internal strain, the flooring material There were problems such as shrinkage over time, which significantly deteriorated the dimensional stability of the flooring material. (Means for solving the problem) In the conventional manufacturing method for laminated flooring, as found in Japanese Patent Publication No. 47-41848, the lamination order of each synthetic resin layer constituting the laminated flooring is not considered. First, various problems as mentioned above have arisen. The present inventors focused on the lamination order of each synthetic resin layer to be laminated, and by making the synthetic resin layer provided on the back side of the fibrous base material a heat-resistant synthetic resin layer,
The present invention was completed based on the discovery that no problem occurs even if the layers are laminated in a specific order. That is, in the method for producing a laminated flooring material of the present invention, a liquid synthetic resin composition is coated and impregnated on a fibrous base material 1 to form an impregnated layer, and this impregnated layer is subjected to a solidification method by heating, ultraviolet irradiation, or electron beam irradiation. 1 or 2 of
By performing the above solidification method, the impregnated layer is solidified to form a heat-resistant synthetic resin layer 2, and the fibers on the opposite side to the application surface of the liquid synthetic resin composition forming this heat-resistant synthetic resin layer 2 are It is characterized in that a soft synthetic resin intermediate layer 3 and a soft synthetic resin top layer 4 are sequentially laminated on the surface of the base material 1. In the laminated flooring material of the present invention, a liquid synthetic resin composition is coated and impregnated on a fibrous base material 1, and a heat-resistant synthetic resin layer 2 is formed by one or more of the solidifying means of heating, ultraviolet irradiation, or electron beam irradiation. Then, a soft synthetic resin intermediate layer 3 is laminated on the surface of the fibrous base material opposite to the surface to which the liquid synthetic resin composition is applied by a calendering method, an extrusion method, a paste coating method, etc. , a printing layer 5 is formed by printing with a gravure printing method, a flexo printing method, a rotary screen printing method, a transfer printing method, etc., and a soft synthetic resin top layer 4 is further applied on this surface by a calendar method, an extrusion method, It is obtained by laminating layers using a paste coating method or the like. Heating, which is one of the above-mentioned solidification means, may be performed using any known heating method, but examples include electric heater, infrared heater, hot air blowing, Elofin, steam injection, high frequency induction heating, high frequency dielectric heating, etc. be able to. Among the above-mentioned resin lamination methods, the paste coating method is common, and here, a method for manufacturing a flooring material using the paste coating method will be described. A liquid synthetic resin composition is coated and impregnated onto the fibrous base material 1, heated at 50°C to 250°C for 30 seconds to 15 minutes to solidify the liquid synthetic resin composition, and then exposed to ultraviolet light or A heat-resistant synthetic resin layer 2 is formed by irradiating with an electron beam, and a vinyl chloride resin plastisol is applied to the surface opposite to the surface to which the liquid synthetic resin composition is applied, and then heated at 120°C to 250°C for 30 seconds to 5 minutes. Heated to form a soft synthetic resin intermediate layer 3, then coated with vinyl chloride resin plastisol and heated at 150°C to 250°C.
After heating for 30 seconds to 5 minutes to melt the vinyl chloride resin plastisol, embossing is performed as necessary, and then irradiation with ultraviolet rays or electron beams is performed as necessary. From the viewpoint of the design of the flooring material, it is preferable to form a printed layer 5 in which an arbitrary pattern is printed on the soft synthetic resin intermediate layer 3. Furthermore, it is possible to perform not only printing but also both printing and embossing, and in this case, it is also possible to perform printing and embossing at the same time, such as valley dyeing embossing and head stain printing. In addition, when the soft synthetic resin intermediate layer 3 is foamed with a chemical foaming agent, a part of the pattern of the printed layer 5 is printed with an ink containing a foaming inhibitor and/or a foaming accelerator, thereby creating a chemical embossment. is also possible. Further, by printing a part of the pattern on the printing layer 5 with foaming ink and/or non-foaming ink, printing and unevenness can be synchronized. As a means for coating and impregnating the liquid synthetic resin composition on the fibrous base material 1, any commonly used method may be used, such as a knife coater, roll coater, gravure printer, rotary screen, curtain flow coater, date coating, etc. is preferred. When applying a liquid synthetic resin composition thinly and uniformly to a fibrous base material 1 such as glass paper with a low density of glass fibers (coarse mesh), it is important to prevent the liquid synthetic resin composition from seeping onto the back side of the glass paper. Gravure printers, roll coaters, rotary screens, etc. are suitable. In addition, the viscosity of the liquid synthetic resin composition is 1
It is necessary to adjust the viscosity appropriately depending on the fiber density and application method. For example, in the case of a fibrous base material 1 with a high fiber density, such as an asbestos sheet, the liquid synthetic resin composition can be applied with a viscosity ranging from low to high, and the appropriateness depends on each application method. The viscosity can be adjusted within the viscosity range, but the liquid synthetic resin composition is applied using a knife coater to a fibrous base material 1 that does not have a high fiber density, such as glass fiber paper with a glass fiber density of about 0.12 g/cc. When coating, the viscosity of the liquid synthetic resin composition is preferably adjusted to about 10,000 CPS to 500,000 CPS. In addition, when using a fibrous base material 1 with a low fiber density (coarse mesh), and even if the liquid synthetic resin composition is applied, the impregnation with the liquid synthetic resin composition is insufficient. When the soft synthetic resin intermediate layer 3 is laminated on the surface opposite to the surface on which the liquid synthetic resin composition is applied, air bubbles will enter the laminated interface, and if these are foamed, abnormalities may occur due to the effects of the air bubbles.
In such a case, the surface opposite to the surface to which the liquid synthetic resin composition is applied is sealed with, for example, vinyl chloride resin paste, or the liquid synthetic resin composition is applied to the fibrous base material 1. It is preferable to laminate the soft synthetic resin intermediate layer 3 after drying, heating and compressing between rolls to smooth the laminated surface. In addition, when the flooring material is adhered to the base to such an extent that it does not peel off during practical use, and when the flooring material is peeled off, it must be peeled off at the interface between the heat-resistant synthetic resin layer 2 on the back side of the flooring material and the adhesive, or The heat-resistant synthetic resin layer 2 is peeled off in such a way that the thin layer of the heat-resistant synthetic resin layer 2 remains on the base together with the adhesive when the heat-resistant synthetic resin layer 2 is destroyed.
Adhesive strength between and adhesive layer or heat-resistant synthetic resin layer 2
The delamination strength due to fracture is 0.3 to 5Kg/2cm
Preferably, the width is the same. If this adhesive strength or interlayer peel strength is less than 0.3 kg/2 cm width, the adhesive strength with the base will be too weak and peeling will occur during practical use, or the adhesive strength or interlayer peel strength will be less than 5.
If the width exceeds Kg/2cm, it becomes difficult to separate the flooring material from the base. ●Fibrous base material The fibrous base material 1 used in the present invention may be a single layer or two or more layers as long as it has excellent dimensional stability such as a felt sheet, woven fabric, knitted fabric, or nonwoven fabric. Although multi-layered ones can be used, in particular, from the viewpoint of dimensional stability, asbestos sheets, sheets mixed with at least two or more types of inorganic and/or organic fibers such as asbestos, glass fiber, paper, and polyester fibers, glass fiber paper, Paper or the like is preferred. Heat-resistant synthetic resin layer <liquid synthetic resin composition> The liquid synthetic resin composition for forming the heat-resistant synthetic resin layer 2 used in the present invention includes a soft synthetic resin intermediate layer 3 and a soft synthetic resin top layer. In lamination processing such as No. 4, it has a heat resistance that does not stick to the heated support in the heating furnace, and it also uses an adhesive for ordinary flooring construction. Does it adhere to an extent that does not cause peeling during practical use even after the flooring is installed, and provides sufficient strength to allow it to be peeled off at the interface between the heat-resistant synthetic resin layer 2 and the adhesive layer when the flooring is peeled off? Alternatively, any material can be used as long as it causes delamination due to destruction of the heat-resistant synthetic resin layer 2 when the flooring material is peeled off. The liquid synthetic resin composition for forming the heat-resistant synthetic resin layer 2 used in the present invention is preferably the following, but the present invention is not limited thereto. A composition in which vinyl chloride paste is blended with a large amount of inorganic and/or organic filler with excellent heat resistance A composition in which vinyl chloride paste is blended with a compound that crosslinks when heated A vinyl chloride paste is irradiated with ultraviolet rays or electron beams, etc. A composition containing a compound that can be crosslinked by the following means: A large amount of an inorganic and/or organic filler with excellent heat resistance in a non-reactive liquid composition such as a non-reactive synthetic resin emulsion or a non-reactive synthetic rubber latex. A composition in which a non-reactive synthetic resin emulsion or a non-reactive liquid composition such as a non-reactive synthetic rubber latex is blended with a compound that crosslinks when heated A non-reactive synthetic resin emulsion or a non-reactive liquid composition A composition in which a non-reactive liquid composition such as a synthetic rubber latex is blended with a compound that crosslinks by means such as ultraviolet irradiation or electron beam irradiation.A reactive liquid composition such as a reactive synthetic resin emulsion or a reactive synthetic rubber latex. Liquid composition comprising a compound that crosslinks upon heating Liquid composition comprising a compound crosslinking upon ultraviolet irradiation or electron beam irradiation When the liquid synthetic resin composition for forming the heat-resistant synthetic resin layer 2 is a composition of This vinyl chloride resin paste composition contains 30 to 130 parts by weight of a plasticizer, an appropriate amount of a stabilizer, and 50 to 400 parts by weight of an inorganic and/or organic filler with excellent heat resistance, per 100 parts by weight of a vinyl chloride resin. It also contains appropriate amounts of viscosity modifiers, colorants, etc., if necessary. If the amount of plasticizer is less than 30 parts by weight based on 100 parts by weight of the vinyl chloride resin, the heat-resistant synthetic resin layer 2 will become too hard and its low-temperature properties will deteriorate, making it difficult to apply in winter, which is not preferable. Furthermore, if the amount of plasticizer exceeds 130 parts by weight per 100 parts by weight of vinyl chloride resin, not only will the heat-resistant synthetic resin layer 2 become extremely sticky, but especially when applied with a synthetic rubber latex adhesive, plasticizer A large amount of the agent migrates to the synthetic rubber adhesive layer, resulting in a significant decrease in adhesive strength.
This is not preferable since it causes problems such as warping and peeling of the flooring material during practical use. The amount of inorganic and/or organic filler with excellent heat resistance is 50 parts by weight per 100 parts by weight of vinyl chloride resin.
If the amount is less than parts by weight, the heat-resistant synthetic resin layer 2
The material sticks to the support while it is heated in the heating furnace, making it impossible to achieve the intended purpose. or,
When the amount of the inorganic and/or organic filler with excellent heat resistance exceeds 400 parts by weight per 100 parts by weight of the vinyl chloride resin, the amount of the filler becomes too large and the heat-resistant synthetic resin layer 2 becomes brittle. This is not preferable because the flooring material becomes easy to break when it is installed. An inorganic and/or organic filler with excellent heat resistance and a larger particle size is more effective in preventing adhesion to a heated support in a heating furnace even when added in a relatively small amount. This is because the larger the particle size, the rougher the surface of the heat-resistant synthetic resin layer 2 and the smaller the contact area with the heated support. This is thought to be due to the arrangement of the inorganic and/or organic fillers with large particle sizes and excellent heat resistance, which prevents adhesion to the heated support. When the liquid synthetic resin composition for forming the heat-resistant synthetic resin layer 2 is the composition, the vinyl chloride resin paste composition contains 10 to 100 parts by weight of a plasticizer per 100 parts by weight of the vinyl chloride resin, Compounds that crosslink by heating, ultraviolet irradiation, electron beam irradiation, etc.
0.5 to 100 parts by weight, an appropriate amount of stabilizer, and, if necessary, a polymerization initiator, photosensitizer, catalyst, viscosity modifier, colorant, foam stabilizer, foaming agent, inorganic material with excellent heat resistance, and and/or an appropriate amount of an organic filler. If the amount of plasticizer is less than 10 parts by weight based on 100 parts by weight of the vinyl chloride resin, the heat-resistant synthetic resin layer 2 will become too hard and its low-temperature properties will deteriorate, making installation in winter difficult and undesirable. . Furthermore, if the amount of plasticizer exceeds 100 parts by weight per 100 parts by weight of the vinyl chloride resin, not only will the heat-resistant synthetic resin layer 2 become extremely sticky;
In particular, when installing with a synthetic rubber latex adhesive, a large amount of plasticizer migrates to the synthetic rubber adhesive layer, significantly reducing the adhesive strength, resulting in problems such as warping and peeling of the flooring material during practical use. , which is not desirable. If the amount of the compound that is crosslinked by means such as heating, ultraviolet irradiation, or electron beam irradiation is less than 0.5 parts by weight per 100 parts by weight of vinyl chloride resin, the degree of crosslinking is low and the compound cannot be heated in the heating furnace. It sticks to a certain support and cannot achieve its intended purpose. In addition, the amount of compounds crosslinked by heating, ultraviolet irradiation, electron beam irradiation, etc.
If the amount exceeds 100 parts by weight, the degree of crosslinking will become too high and the heat-resistant synthetic resin layer 2 will become hard and brittle, making it impractical. When the liquid synthetic resin composition for forming the heat-resistant synthetic resin layer 2 is a composition of It consists of 150 to 950 parts by weight of an inorganic and/or organic filler with excellent heat resistance per 100 parts by weight, and, if necessary, appropriate amounts of a viscosity modifier, a coloring agent, etc. The amount of inorganic and/or organic fillers with excellent heat resistance depends on the amount of synthetic resin or synthetic rubber contained in the emulsion or latex.
If the amount is less than 150 parts by weight relative to 100 parts by weight, the heat-resistant synthetic resin layer 2 will stick to the heated support in the heating furnace, making it impossible to achieve the intended purpose. . In addition, the amount of inorganic and/or organic fillers with excellent heat resistance depends on the amount of synthetic resin or synthetic rubber contained in the emulsion or latex.
If the amount exceeds 950 parts by weight relative to 100 parts by weight, the heat-resistant synthetic resin layer 2 becomes brittle and the flooring material tends to break during installation, which is not preferable. When the liquid synthetic resin composition for forming the heat-resistant synthetic resin layer 2 is a composition of
10 to 100 parts by weight of a compound crosslinked by heating, ultraviolet irradiation, electron beam irradiation, etc., per 100 parts by weight;
It also contains appropriate amounts of polymerization initiators, photosensitizers, catalysts, viscosity modifiers, colorants, foam stabilizers, and inorganic and/or organic fillers with excellent heat resistance, as required. If the amount of the compound crosslinked by heating, ultraviolet irradiation, electron beam irradiation, etc. is less than 10 parts by weight per 100 parts by weight of the synthetic resin or synthetic rubber contained in the non-reactive liquid composition, etc. The degree of crosslinking of the heat-resistant synthetic resin layer is low and it sticks to the support while it is heated in the heating furnace, making it impossible to achieve the intended purpose. In addition, if the amount of the compound crosslinked by means such as heating, ultraviolet irradiation, or electron beam irradiation exceeds 100 parts by weight per 100 parts by weight of the synthetic resin or synthetic rubber contained in the emulsion or latex, the degree of crosslinking will decrease. If it becomes too high, the heat-resistant synthetic resin layer 2 becomes hard and brittle, making it impractical. Additionally, the addition of inorganic and/or organic fillers with excellent heat resistance may improve adhesion to adhesives for floor construction. When the liquid synthetic resin composition for forming the heat-resistant synthetic resin layer 2 is a composition of It consists of appropriate amounts of a regulator, a foam stabilizer, a colorant, an inorganic and/or organic filler with excellent heat resistance, etc. The above reactive synthetic resin emulsion,
If the synthetic rubber latex or the like is self-crosslinking, it will crosslink alone to form the heat-resistant synthetic resin layer 2, but if the heat resistance is to be further improved, the addition of a crosslinking agent is effective. Additionally, the addition of inorganic and/or organic fillers with excellent heat resistance may improve the adhesive properties of adhesives for floor construction. When the liquid synthetic resin composition for forming the heat-resistant synthetic resin layer is a composition of It comprises appropriate amounts of a polymerization initiator, photosensitizer, catalyst, colorant, inorganic and/or organic filler with excellent heat resistance, and the like. Addition of an inorganic and/or organic filler with excellent heat resistance to the liquid compound that is crosslinked by means such as heating, ultraviolet irradiation, or electron beam irradiation can also improve adhesion to adhesives for floor construction. be. <Conditions for solidifying the liquid synthetic resin composition> The following methods are suitable for solidifying the liquid synthetic resin composition for forming the heat-resistant synthetic resin layer 2, but the present invention is not limited thereto in any way. It is not something that will be done. In the case of a composition of 120% of the liquid synthetic resin composition
Preheat at 180°C to 180°C for 30 seconds to 6 minutes to make it semi-solid, then heat at 180°C to 250°C for 30 seconds to 5 minutes to melt the vinyl chloride resin, or preheat as described above. It is preferable to heat the liquid synthetic resin composition at 180° C. to 250° C. for 30 seconds to 5 minutes to melt the vinyl chloride resin. In the case of the composition, heating is performed under the same conditions as in the case of the above-mentioned composition to melt the vinyl chloride resin and crosslink the compound to be crosslinked. In the case of the above composition as well, it is preferable that the vinyl chloride resin be melted by heating under the same conditions as the above composition, and then crosslinked by irradiation with ultraviolet rays or electron beams. In the case of a composition, the liquid synthetic resin composition is heated to 50℃.
It is preferable to heat dry at ~180°C for 30 seconds to 15 minutes. In the case of a composition, the liquid synthetic resin composition is heated to 50℃.
~100℃ after heating and drying at ~150℃ for 30 seconds ~ 15 minutes
The liquid synthetic resin composition is heated at 200°C for 30 seconds to 10 minutes to crosslink, or the liquid synthetic resin composition is heated at 100°C to 200°C for 30 minutes.
It is preferable to heat for 15 seconds to 15 minutes to effect crosslinking.
In the case of emulsions and latexes, if they are heated at high temperatures from the beginning, they tend to foam abnormally due to the influence of moisture. In such cases, the two-stage heating described above is preferable, and if there are no such problems, the above-mentioned method can be used. A one-stage heating method is efficient. In the case of a composition of 50%, the liquid synthetic resin composition is
It is preferred that the compound be crosslinked by heating and drying at a temperature of 180°C to 180°C for 30 seconds to 15 minutes and then irradiating it with ultraviolet rays or electron beams. In the case of the composition, it is preferable to carry out crosslinking under the same conditions as in the case of the above-mentioned composition. In the case of the composition, crosslinking is preferably carried out by heating at 50°C to 200°C for 30 seconds to 15 minutes. In the case of the composition, the liquid compound can be crosslinked and cured in a shorter time by irradiating the liquid compound with ultraviolet rays or electron beams. If this compound contains a dispersion medium such as water or a solvent, it is preferable to heat the compound in advance to remove the dispersion medium before irradiating it with ultraviolet rays or electron beams. Ultraviolet irradiation can be performed using a low-pressure mercury lamp, medium-pressure mercury lamp, high-pressure mercury lamp, or ultra-high pressure mercury lamp, and the ultraviolet irradiation time can be varied depending on the strength of the mercury lamp used. That is, when the intensity of the mercury lamp is strong, the irradiation time can be shortened, whereas when the intensity of the mercury lamp is weak, the irradiation time needs to be lengthened. Furthermore, when irradiating with ultraviolet rays, it is preferable that the liquid synthetic resin composition be transparent or semi-transparent, and it is difficult to irradiate ultraviolet rays with opaque compositions. When the liquid synthetic resin composition is opaque, it is preferable to perform electron beam irradiation. Furthermore, the production speed of electron beam irradiation is faster than that of ultraviolet irradiation, and even opaque synthetic resin compositions containing a large amount of filler can be crosslinked. is more advantageous. <Thickness of the heat-resistant synthetic resin layer> Thickness of the heat-resistant synthetic resin layer 2 obtained by coating and impregnating the fibrous base material 1 with a liquid synthetic resin composition (the thickness of the heat-resistant synthetic resin layer 2 obtained by coating and impregnating the fibrous base material 1 with a liquid synthetic resin composition) If the flooring material peels off at the interface between the heat-resistant synthetic resin layer and the adhesive layer, the thickness (the thickness of the impregnated material excluding the thickness of the fibrous base material 1) shall be 3.0 m/m or less. It is preferable to do so. The liquid synthetic resin composition is a fibrous base material 1
If the heat-resistant synthetic resin layer 2 is sufficiently impregnated with the above-mentioned thickness, there is no particular problem with the thickness of the heat-resistant synthetic resin layer 2.
For example, in the case of asbestos sheets, if the thickness of the heat-resistant synthetic resin layer 2 is 0.02 m/m or less, part of the asbestos sheet may remain on the base when the flooring material is removed. In such cases, the thickness of the heat-resistant liquid synthetic resin layer 2 is preferably 0.02 to 3.0 m/m. Although there is no particular restriction on the upper limit of the thickness of the heat-resistant synthetic resin layer 2,
If the thickness of the heat-resistant synthetic resin layer 2 exceeds 3.0 m/m, the resulting flooring material will be very thick, which is inconvenient for construction and is not very desirable. Further, in the case where the flooring material peels off due to delamination due to destruction of the heat-resistant synthetic resin layer 2, the thickness of the heat-resistant synthetic resin layer 2 is preferably 0.5 m/m or less. When the thickness of the heat-resistant synthetic resin layer 2 is 0.5 m/m or more,
This is because when the flooring material is peeled off, the unevenness of the base becomes large, and it becomes impossible to construct the flooring material thereon in that state, making it impossible to achieve the intended purpose of the present invention. Also, from the point of view of reducing the weight of the flooring itself, the heat-resistant synthetic resin layer 2 can be foamed, but if the foaming ratio is increased, the foam layer will break when the flooring is peeled off, so the density of the foamed layer will be lower. It is preferable that the amount is 0.2 g/cc or more. As a method for forming the foam layer, a method using a chemical foaming agent, a method using mechanical foaming, etc. can be used. - Soft synthetic resin intermediate layer <composition> The soft synthetic resin composition for forming the soft synthetic resin intermediate layer 3 used in the present invention may be any material as long as it can withstand use as a flooring material, but vinyl chloride It is common to use resin paste,
The vinyl chloride resin paste composition will be described below. The vinyl chloride resin paste composition for forming the soft synthetic resin intermediate layer is made of vinyl chloride resin.
From 20 to 120 parts by weight of plasticizer, an appropriate amount of stabilizer, and, if necessary, appropriate amounts of viscosity modifier, foaming agent, foam stabilizer, coloring agent, filler, metal powder, etc. per 100 parts by weight. Become. If the amount of plasticizer is less than 20 parts by weight based on 100 parts by weight of the vinyl chloride resin, the soft synthetic resin intermediate layer 3 will become too hard, resulting in poor low-temperature properties (especially flexibility at low temperatures) and poor performance in winter. This is not desirable as it makes construction difficult. On the other hand, if the amount of plasticizer exceeds 120 parts by weight per 100 parts by weight of vinyl chloride resin, the transfer of the plasticizer from the soft synthetic resin intermediate layer 3 to the soft synthetic resin top layer 4 will increase, causing the surface of the flooring material to deteriorate. This is not preferable since it has the drawback that it becomes extremely sticky, resulting in increased contamination of the surface of the flooring material. Furthermore, it is advantageous in terms of construction and cost to foam the soft synthetic resin intermediate layer 3 unless there is a special reason. Foaming methods include a method in which a chemical foaming agent is added to the vinyl chloride resin paste and the chemical foaming agent is decomposed by heating to cause foaming, and a method in which a foam stabilizer is added to the vinyl chloride resin paste to create a foam mechanically. , and a method of adding the vinyl chloride resin paste and a hollow balloon-like substance, and any of these methods can be used in the present invention. The amounts of the chemical foaming agent, foam stabilizer, and hollow balloon-like substance are adjusted as necessary. In addition, in order to improve the cigarette ignition resistance of the flooring material, it is necessary to increase the thermal conductivity of the soft synthetic resin intermediate layer 3, and in this case, the soft synthetic resin intermediate layer 3 should have a non-foamed structure. There is a need. In this case, by adding an inorganic filler and/or a metal powder, etc., the thermal conductivity of the soft synthetic resin intermediate layer 3 is increased, and the cigarette ignition resistance of the flooring material is considerably improved. The amount of inorganic filler added is preferably 400 parts by weight or less per 100 parts by weight of vinyl chloride resin, and the amount of metal powder added is preferably 400 parts by weight or less per 100 parts by weight of vinyl chloride resin.
It is preferably 600 parts by weight or less. Of course, it is also possible to use an inorganic filler and metal powder together. If the amount of inorganic filler exceeds 400 parts by weight per 100 parts by weight of vinyl chloride resin,
The mechanical strength of the soft synthetic resin intermediate layer 3 becomes weaker,
This is not preferable because it becomes weak against bending and the weight of the flooring material itself becomes heavy, resulting in poor workability.
Furthermore, if the amount of metal powder exceeds 600 parts by weight per 100 parts by weight of vinyl chloride resin, the mechanical strength of the soft synthetic resin intermediate layer 3 will be weakened, making it weak against bending and making the flooring material heavier. This is not preferable because it impairs workability. <Thickness of the soft synthetic resin intermediate layer> The thickness of the soft synthetic resin intermediate layer 3 is generally 0.05 m/
m to 4.00 m/m, but is not particularly limited to this range. However, if the thickness of the soft synthetic resin intermediate layer 3 exceeds 4.00 m/m, the resulting flooring material will be very thick, which is inconvenient for construction and is not very preferable. Further, the soft synthetic resin intermediate layer 3 may be a foamed layer or a non-foamed layer. However, if the soft synthetic resin intermediate layer 3 is made of a non-foamed layer, the weight of the flooring material will be heavy and transportation and construction of the flooring material will be inconvenient, so it is better to use a foamed layer unless there is a special reason. In addition, methods for forming a foam layer include a method using a chemical foaming agent and a method using mechanical foaming, but when performing chemical embossing, a method using a chemical foaming agent is required.
In other cases, mechanical foaming can also be used. ●Soft synthetic resin top layer <composition> The soft synthetic resin composition for forming the soft synthetic resin top layer 4 used in the present invention has excellent mechanical strength and is suitable for use as a top layer of flooring materials. Any material may be used as long as it is durable, but vinyl chloride paste is generally used, and the vinyl chloride resin paste composition will be described below. The vinyl chloride resin paste composition for forming the soft synthetic resin top layer 4 contains 10 to 100 parts by weight of a plasticizer, an appropriate amount of a stabilizer, and, if necessary, a viscosity of 100 parts by weight of a vinyl chloride resin. It consists of appropriate amounts of a modifier, a colorant, a filler, a compound crosslinkable by means such as ultraviolet irradiation or electron beam irradiation, and a photosensitizer. If the amount of plasticizer is less than 10 parts by weight based on 100 parts by weight of vinyl chloride resin, the soft synthetic resin top layer 4 will become too hard, the surface will be slippery as a flooring material, and the low-temperature properties (especially The flexibility at low temperatures deteriorates, making construction difficult in winter, which is not preferable. On the contrary, the amount of plasticizer is vinyl chloride resin
If the amount exceeds 100 parts by weight, the surface of the flooring material becomes extremely sticky, and as a result, the surface of the flooring material becomes seriously contaminated, which is not preferable. When printing is performed on the surface of the soft synthetic resin intermediate layer 4, the soft synthetic resin top layer 4 needs to be transparent or translucent; however, in other cases, the soft synthetic resin top layer 4 4 may be opaque, and in this case, it is more advantageous in terms of cost to use a filler. In addition, in order to improve the cigarette flame resistance of the flooring material, it is necessary to improve the heat resistance of the soft synthetic resin top layer 4, and in this case, it is necessary to improve the heat resistance of the soft synthetic resin top layer 4. It is necessary to add a crosslinking compound and, if necessary, a photosensitizer and the like to the vinyl chloride resin paste composition for forming the soft synthetic resin top layer 4. When the means for crosslinking the compound contained in the soft synthetic resin top layer 4 that is crosslinked by ultraviolet irradiation, electron beam irradiation, etc. is ultraviolet irradiation, it is better to use a photosensitizer in combination. When the means for crosslinking the compound is electron beam irradiation, there is no need to use a photosensitizer together. The amount of the compound crosslinked by means such as ultraviolet irradiation or electron beam irradiation is preferably 10 to 100 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the amount of the compound crosslinked by means such as ultraviolet irradiation or electron beam irradiation is less than 10 parts by weight per 100 parts by weight of vinyl chloride resin, the degree of crosslinking will be low and the cigarette flame resistance will be poor and the intended purpose will not be met. It is unattainable.
On the other hand, if the amount of the compound crosslinked by means such as ultraviolet irradiation or electron beam irradiation exceeds 100 parts by weight per 100 parts by weight of vinyl chloride resin, the degree of crosslinking will be too high and the surface of the flooring material will become too hard and slippery. Not only that, but the flooring also warps during use, making it impractical. <Thickness of the soft synthetic resin top layer> The thickness of the soft synthetic resin top layer 4 is 0.05 m/m ~
2.00m/m is preferred. If the thickness of the soft synthetic resin top layer 4 is less than 0.05 m/m, the soft synthetic resin top layer 4 will quickly wear out due to people walking, etc., and the life of the flooring material will be shortened. Undesirable.
Furthermore, if the thickness of the soft synthetic resin top layer 4 exceeds 2.00 m/m, the floor material itself becomes hard, which is inconvenient to install, and it also tends to warp or shrink, which is not very preferable. <Aspects of the soft synthetic resin top layer> The soft synthetic resin top layer 4 may be colorless and transparent, transparent or opaque colored in any color, and from the viewpoint of the design of the flooring material, the soft synthetic resin top layer 4 may be made of a soft synthetic resin top layer. The coating layer 4 may contain monochromatic or multi-colored synthetic resin powder, chips, lumps, etc. colored in any desired color. When monochromatic or multi-colored synthetic resin powder, chips, lumps, etc. colored in any color are transparent or translucent, they may be mixed with the printed pattern on the surface of the soft synthetic resin intermediate layer 3. If a mosaic design is expressed and the synthetic resin powder, chips, lumps, etc. of a single color or multiple colors colored in any color are opaque, the synthetic resin powder, chips, etc. , a unique design is expressed by lumps, etc. Furthermore, by imparting heat resistance to the soft synthetic resin top layer 4, even if a lit cigarette is left on the surface of the flooring material or a lit cigarette is smudged on the surface of the flooring material, the surface of the flooring material will remain intact. To provide a cigarette flame-resistant flooring material that does not discolor or cause scorch marks. A method for imparting heat resistance to the soft synthetic resin top layer 4 is to mix a soft synthetic resin composition with a compound that crosslinks by heating, ultraviolet irradiation, electron beam irradiation, etc. Although there are methods of crosslinking using ultraviolet irradiation or electron beam irradiation, methods of crosslinking using ultraviolet irradiation or electron beam irradiation are preferred from the viewpoint of crosslinkability. Further, when embossing is performed on the soft synthetic resin top layer 4, it is preferable to perform the embossing before irradiation with ultraviolet rays or electron beams. In order to improve the cigarette ignition resistance of the flooring material, as mentioned above, the soft synthetic resin top layer 4 is given heat resistance, and the soft synthetic resin intermediate layer 3 and the heat-resistant synthetic resin layer 2 are made of a non-foamed structure. It is preferable to mix a large amount of filler and/or metal powder to improve the heat conduction of the floor material itself. ●Compounds and additives used in the present invention <vinyl chloride resin> Heat-resistant synthetic resin layer 2, soft synthetic resin intermediate layer 3,
The vinyl chloride resin used in the vinyl chloride resin paste composition for forming the soft synthetic resin top layer 4 includes commonly used emulsion polymerized vinyl chloride resins, suspension polymerized vinyl chloride resins, bulk polymerized vinyl chloride resins, etc. Vinyl chloride resin can be used. Also,
In addition to vinyl chloride homopolymer, vinyl acetate,
Copolymers of vinyl chloride and one or more of ethylene, alkyl ethers, acrylic esters, methacrylic esters, etc. can also be used, and these homopolymers and copolymers can be used alone or in combination. Also, other polymers can be blended with the vinyl chloride resins as described above. Examples of resins that can be blended include, but are not limited to, acrylonitrile-butadiene copolymers, ethylene-vinyl acetate copolymers, acrylonitrile-butadiene-styrene copolymers, and acrylic resins. <Plasticizer> As the plasticizer, commonly used plasticizers can be used, examples of which are listed below. Phthalate ester plasticizers include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, octyl capryl phthalate, dicyclohexyl phthalate, didodecyl phthalate, butyl benzyl phthalate, dimethyl glycol phthalate, ethyl phthalyl ethyl glycolate, Methylphthalyl ethyl glycolate, butylphthalyl butyl glycolate, diisodecyl phthalate, etc. are used. Examples of phosphorous ester plasticizers include tributyl phosphate, tricresyl phosphate, triphenyl phosphate, trichloroethyl phosphate, trioctyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, arylalkyl phosphate, Diphenyl monoorthoxenyl phosphate and the like are used. Examples of fatty acid ester plasticizers include methyl acetyl ricinoleate, dioctyl adipate, dioctyl azelate, dibutyl sebacate, dioctyl sebacate, triacetyl glycerin, glycerol butyrate, diisodecyl succinate, diisodecyl adipate, succinic acid mixed alkyl ester, etc. used. In addition, trimellitic acid ester plasticizers such as trioctyl trimellitic acid, epoxy plasticizers such as epoxidized soybean oil and various epoxy resins, polyester polymer plasticizers, etc. can also be used. Furthermore, for the purpose of reducing the viscosity of the vinyl chloride resin paste, small amounts of viscosity modifiers such as gasoline, octane, benzene, toluene, naphtha,
A volatile diluent such as a dodecylbenzene derivative or a viscosity reducing agent such as various surfactants may be used in combination with the plasticizer. <Stabilizer> Any stabilizer that is normally used for vinyl chloride resin can be used. Specifically, in addition to metal stabilizers such as cadmium, zinc, barium, calcium, strontium, aluminum, magnesium, cerium, sodium, lead, and tin,
Organic phosphorus compounds, polyhydric alcohols, epoxy compounds, etc. can be used alone or in combination of two or more. The amount of the stabilizer added is preferably 0.1 to 10 parts by weight per 100 parts by weight of the vinyl chloride resin. <Synthetic resin emulsion, synthetic rubber latex> Any commonly used non-reactive synthetic resin emulsion or synthetic rubber latex can be used. Specifically, vinyl chloride resin emulsion, vinyl chloride-ethylene copolymer emulsion, vinyl chloride-vinylidene chloride copolymer emulsion, vinyl chloride-vinyl acetate copolymer emulsion, vinylidene chloride resin emulsion, vinyl acetate resin emulsion, and acetic acid. Synthetic resin emulsions such as vinyl-acrylic copolymer emulsion, ethylene-vinyl acetate copolymer emulsion, acrylic resin emulsion, acrylic-styrene copolymer emulsion, urethane resin emulsion, or SBR latex, NBR latex, CR latex, IIR Synthetic rubber latex such as latex can be used. These may be used alone or in combination of two or more. In addition to the above emulsions and latexes, solutions of synthetic resins and synthetic rubbers dissolved in organic solvents or water can also be used in the same way as the above emulsions and latexes. Any commonly used synthetic resin emulsion or synthetic rubber latex can be used, but specifically, reactive groups such as carboxyl groups, hydroxyl groups, and amide groups are introduced into the emulsion or latex polymer. Products that are heat-crosslinked by adding an initial condensate of melamine or urea as a crosslinking agent, or products that have reactive groups such as glycidyl groups or methylol groups introduced into emulsions or latex polymers, such as acrylic esters or methacrylic esters. An emulsion obtained by copolymerizing the main component with glycidyl acrylate or glycidyl methacrylate and tert-butyl or amyl acrylate, or an emulsion obtained by copolymerizing styrene acrylate and acrylamide and then adding methylol Self-crosslinking emulsions and latexes such as emulsions obtained by oxidation can be used. Reactive synthetic resin emulsions and synthetic rubber latexes include acrylic resin emulsions, vinyl acetate resin emulsions, vinyl acetate-acrylic copolymer emulsions, vinyl chloride-vinyl acetate copolymer emulsions, SBR latexes, NBR latexes, CR latexes, etc. It is raised. These may be used alone or in combination of two or more. It is also possible to use these reactive synthetic resin emulsions and synthetic rubber latexes in combination with the non-reactive synthetic resin emulsions and synthetic rubber latexes.
In addition to the above-mentioned emulsions and latexes, solutions of synthetic resins and synthetic rubbers having the above-mentioned reactive groups dissolved in organic solvents or water can also be used in the same manner as the above-mentioned emulsions and latexes. <Compounds that crosslink by heating, ultraviolet rays, or electron beam irradiation> The following compounds can be used as compounds that crosslink by heating, ultraviolet irradiation, electron beam irradiation, etc., but the present invention is not limited to these in any way. isn't it. ethylene glycol, propylene glycol,
Acrylic acid or methacrylic acid and aliphatic polyhydric alcohol such as butylene glycol, 1,6-hexanediol, neopentyl glycol, polyethylene glycol, polypropylene glycol, trimethylolpropane, trimethylolmethane, glycerin, pentaerythritol, dipentaerythritol, etc. Acrylic polyfunctional compound obtained from; triallylisocyanurate, tris-
Isocyanurate derivatives such as (2-methacryloyl.oxyethyl)-isocyanurate; bisphenol A type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, etc. with at least two or more epoxy groups in one molecule. An acrylic modified epoxy resin obtained from an epoxy compound containing a polyvalent cycloacetal compound and an unsaturated monobasic acid; a reaction product of a polyhydric cycloacetal compound and a glycol unsaturated monocarboxylic acid monoester or a polyhydric alcohol unsaturated monocarboxylic acid ester monool. There are certain unsaturated cycloacetal resins; acrylic-modified polyester resins such as oligoester acrylate; acrylic-modified polyurethane resins; unsaturated polyester resins; diallyl phthalate, etc., and these may be used alone or in combination of several kinds. Furthermore, monofunctional monomers such as styrene monomers, methacrylic acid ester monomers, and acrylic ester monomers may be used in combination with the above-mentioned polyfunctional compounds as reactive thinning agents. The amount of the polyfunctional compound added is preferably 10 to 100 parts by weight per 100 parts by weight of the resin. <Polymerization initiator, catalyst> As the polymerization initiator, commonly used ones can be used. For example, methyl ethyl ketone peroxide, cyclohexanone peroxide, t-butyl hydroperoxide, cumene hydroperoxide, di-t-butyl peroxide,
t-Butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl 2,5-di(t-
butylperoxy)hexane, 2,5-dimethyl2,5-di(t-butylperoxy)hexane,
1,3-bis(t-butylperoxyisopropyl)benzene, 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane,
n-butyl 4,4-bis(t-butylperoxy)valate, benzoyl peroxide, p-
Organic peroxides such as chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, t-butyl peroxybenzoate, and t-butyl peroxyisopropyl carbonate are common, and these can be used alone or in combination of two or more. and use it. Further, as the catalyst, amines such as dimethylaniline and dimethyl para-toluidine, and metal compounds such as cobalt naphthenate and zinc naphthenate are generally used. The amount of polymerization initiator added is 0.5 to 10% of the polyfunctional compound.
Weight % is appropriate. <Photosensitizer> As the photosensitizer, commonly used ones can be used. For example, benzoin, a-methylbenzoin, a-allylbenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, benzophenone, p-bromobenzophenone, 4.4' -tetramethyldiaminobenzophenone, diphenyl disulfide, benzyl, etc., and these can be used alone or in combination of two or more. The amount of photosensitizer added depends on the amount of the polyfunctional compound.
0.5% to 10% by weight is suitable. Further, when the polyfunctional compound is crosslinked by electron beam irradiation, it is not necessary to use a photosensitizer or the like. <Crosslinking agent> In addition to the above polyfunctional compounds, halogenated synthetic resin compositions, such as vinyl chloride resin, copolymers of vinyl chloride and vinyl acetate, ethylene, alkyl ethers, acrylic esters, methacrylic esters, etc., vinylidene chloride When using a synthetic resin composition such as resin or chloroprene rubber, 2-dibutylamino-4,6-dithiocyanuric acid, 2-dicyclohexylamino-4,6-
Dithiocyanuric acid, 2-dibenzylamino-4.
6-dithiocyanuric acid, 2-diphenylamino-
4,6-dithiocyanuric acid, 2-anilino-4.
A crosslinking agent such as 6-dithiocyanuric acid or a metal salt of such a dithiocyanuric acid derivative, and, if necessary, an acid acceptor such as magnesium oxide, calcium oxide, zinc oxide, barium oxide, lead oxide, calcium carbonate, and the like. , a crosslinking accelerator, etc. can also be added. The amount of the crosslinking agent added is preferably 0.5 to 20 parts by weight based on 100 parts by weight of the halogenated synthetic resin. As a crosslinking agent that is added to synthetic resin emulsion or synthetic rubber latex as necessary, an initial condensate of melamine or urea is used, but the present invention is not limited to these in any way. . <Fillers with excellent heat resistance> Inorganic and/or organic fillers with excellent heat resistance are basically those that do not undergo physical or chemical changes such as melting or decomposition at processing temperatures. You can use anything, but here is an example. Calcium carbonate, magnesium carbonate, clay, talc, silica, diatomaceous earth, silica sand, pumice powder, slate powder, mica powder, asbestos, aluminum hydroxide, aluminum oxide, aluminum sulfate, barium sulfate, calcium sulfate, glass bulbs, foaming Inorganic fillers such as glass bulbs, fly ash bulbs, volcanic glass hollow bodies (shirasu balloons), powdered cellulose (cellulose powder), polyvinyl alcohol fibers, cork powder, wood powder, thermosetting resin powder, thermosetting resin hollow spheres Organic fillers such as can be used. <Chemical foaming agent> As the chemical foaming agent used in the present invention, commonly used chemical foaming agents can be used, and examples thereof are listed below. N・N′-dinitrosopentamethylenetetramine, N・N′-dimethyl-N・N′-dinitrosoterephthalamide, azodicarbonamide, azobisisobutyronitrile, benzenesulfonylhydrazide, P・P′-oxybis( benzenesulfonylhydrazide), benzene-1,3-disulfonylhydrazide, toluenesulfonylhydrazide, and the like. <Foam stabilizer> When forming a foam layer by mechanical foaming, it is preferable to use a foam stabilizer, but any commonly used foam stabilizer can be used, such as methylsiloxane emulsion. , methylsiloxane, silicone foam stabilizers such as xylene solutions, fluorine foam stabilizers, fatty acid condensates, alkylaryl sulfonates, metal soaps of oleic and sericinoleic acids, guanidine salts, quaternary ammonium compounds, aldehyde-amines condensation products etc. are used. <Viscosity modifier> Viscosity modifiers are broadly classified into thinners and thickeners.
As the viscosity reducing agent, commonly used ones can be used, examples of which are listed below. If the liquid synthetic resin composition is an oil dispersion system such as vinyl chloride resin plastisol or a solution of synthetic resin or synthetic rubber dissolved in an organic solvent, gasoline, octane, benzene, toluene, xylene, naphtha, dodecylbenzene derivatives, methyl ethyl ketone, Volatile diluents such as methyl isobutyl ketone, various surfactants, etc. are used, and when the liquid synthetic resin composition is an aqueous dispersion system such as a synthetic resin emulsion, synthetic rubber latex, or an aqueous solution of synthetic resin or synthetic rubber, Alcohols such as water, methanol, ethanol, and isopropyl alcohol are used. In addition, commonly used thickeners can be used, examples of which are listed below. When the liquid synthetic resin composition is an oil dispersion system as described above, metal soaps such as aluminum stearate, aluminum oleate, zinc stearate, silica, bentonite, polymerized oil, etc. are used. In the case of water dispersion systems such as silica, bentonite, chemically modified precipitated calcium carbonate, ammonium salts of polymeric organic acids, water-soluble acrylic polymers, acrylic emulsion copolymers, crosslinked acrylic emulsion copolymers,
Ammonium, polymethacrylate, ammonium polyacrylate, sodium polyacrylate, modified sodium polyacrylate, partially oxidized polyacrylate, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, cellulose sodium glycolate, polyvinyl alcohol, ammonia water, etc. are used. I can do it. When adjusting the viscosity of a liquid synthetic resin composition to a viscosity suitable for processing, these viscosity modifiers are added in an appropriate amount as necessary. (Examples) Examples are given below to explain the present invention in more detail, but the present invention is not limited to these Examples. <Formulation Examples> Typical formulation examples and comparative formulation examples of liquid synthetic resin compositions for forming the heat-resistant synthetic resin layer 2 are shown in the table below.
1 and Table 2. Table 3 shows typical blending examples of the vinyl chloride resin composition for forming the soft synthetic resin intermediate layer 3, and further shows typical blending examples of the vinyl chloride resin composition for forming the soft synthetic resin top layer 4. Examples of formulations are shown in Table 4. In addition, an example of production to obtain the acrylic modified polyester resin used in Tables 1 and 4 below is shown. That is, 304 g of tetrahydrophthalic anhydride, 318 g of diethylene glycol, 144 g of acrylic acid,
Toluene 2000c.c., 98% sulfuric acid in an amount equivalent to 2.5% by weight based on the total amount excluding toluene, and phenothiazine in an amount equivalent to 0.08% by weight based on acrylic acid were added, and the mixture was stirred at about 110°C. At the same time, water produced by the esterification reaction was flowed out of the system as an azeotrope with toluene. After about 8 hours, almost the theoretical amount of water flowed out, so the reaction was stopped and the reactor was cooled. The resulting reaction mixture was washed with 1200 c.c. of an aqueous solution containing 3% by weight ammonia and 20% by weight ammonium sulfate,
After washing with an aqueous solution containing 20% by weight of ammonium sulfate, 0.1 g of hydroquinone was added to the toluene layer and the toluene was removed at 50° C. under a reduced pressure of 6 mmHg to obtain acrylic modified polyester resin C. The obtained acrylic modified polyester resin C was a pale yellow liquid with a viscosity of 4250 centipoise (25° C.) and an acid value of 0.18, and an acryloyl group equivalent of 347.

【table】

【table】

【table】

【table】

[Table] Example 1 On glass fiber paper with a dense fiber structure of 0.25 m/m, the vinyl chloride resin paste of Formulation Example 1 was applied to a thickness of 0.20 m/m using a doctor knife coater, and the paste was coated in a heating furnace. Heat and solidify at 200°C for 2 minutes to form a heat-resistant synthetic resin layer, cool and then roll up. and,
Apply the vinyl chloride resin paste of Formulation Example 10 to a thickness of 0.50 m/m using a doctor knife coater on the side opposite to the applied side of the above vinyl chloride resin paste, and heat in a heating oven at 180°C for 1 minute. After solidifying,
After printing a predetermined pattern on this surface using a gravure printing machine, the vinyl chloride resin paste of Formulation Example 12 was applied to a thickness of 0.30 m/m using a doctor knife coater, and then placed in a heating oven at 200°C for 3 minutes. Heat and foam,
After cooling, it was rolled up to obtain a flooring material with a total thickness of 2.0 m/m. At this time, the heat-resistant synthetic resin layer formed from the vinyl chloride resin paste of Formulation Example 1 was
Even when it came into contact with the support heated to 200° C. in the heating furnace, it did not stick to it and easily passed through the heating furnace to obtain the above-mentioned flooring material. This flooring material was pasted on with a synthetic rubber latex adhesive, dried for about a week, and then peeled off. As a result, it was confirmed that it could be peeled off cleanly from the interface between the heat-resistant synthetic resin layer and the adhesive layer. done. Also, cut this flooring material into a size of 200m/m x 200m/m, and
It was pasted on a 300m/m x 300m/m plywood board using a synthetic rubber latex adhesive, dried at room temperature for 7 days, and then left at a temperature of 70°C for 200 hours.
As a result of observing whether the flooring material is warped or not,
No warping was observed, and it was confirmed that this flooring material had the basic characteristics required as a removable flooring material. The test results are shown in Table-5. Examples 2 to 3 A heat-resistant synthetic resin layer was formed on glass fiber paper with a dense fiber structure of 0.25 m/m using the vinyl chloride resin paste of Formulation Examples 2 to 3 under the same conditions as in Example 1, and then cooled. Rewind later. Then, apply the vinyl chloride resin paste of Formulation Example 10 to a thickness of 0.5 m/m on the side opposite to the applied side of the vinyl chloride paste,
After solidifying by heating at 180°C for 1 minute in a heating furnace, printing was performed in the same manner as in Example 1, and then the vinyl chloride resin paste of Formulation Example 12 was applied to the surface with a thickness of 0.3 m/m, A flooring material was created under the same conditions as in Example 1. The heat-resistant synthetic resin layers formed from the vinyl chloride resin pastes in Formulation Examples 2 and 3 above do not stick easily even when they come into contact with the support heated to 200°C in the heating furnace. The floor material was passed through a heating furnace to obtain the above-mentioned flooring material. These flooring materials were tested for releasability and warping in the same manner as in Example 1, and the results showed that all of these flooring materials had the basic performance necessary as a removable flooring material. was confirmed. The test results are shown in Table-5. Example 4 The vinyl chloride resin paste of Formulation Example 4 was applied to a thickness of 0.20 m/m using a doctor knife coater on glass fiber paper with a dense fiber structure of 0.25 m/m.
After heating and solidifying in a heating furnace at 200℃ for 2 minutes,
Using three 80W/cm high-pressure mercury lamps, irradiation distance 15
Ultraviolet rays are irradiated at a speed of 6 m/min to form a heat-resistant synthetic resin layer and the film is wound up. Then, the vinyl chloride resin paste of Formulation Example 10 was applied to the surface opposite to the surface to which the vinyl chloride resin paste was applied at a thickness of 0.5 m/m using a doctor knife coater, and heated in a heating oven at 180°C for 1 minute. After solidification, a predetermined pattern was printed on the surface using a gravure printing machine, and then the vinyl chloride resin paste of Formulation Example 12 was applied to a thickness of 0.30 m/m using a doctor knife coater, and then heated to a thickness of 200 m/m in a heating furnace. The mixture was heated and foamed at ℃ for 3 minutes, cooled, and then rolled up to obtain a flooring material with a total thickness of 2.0 m/m. At this time, the heat-resistant synthetic resin layer formed from the vinyl chloride resin paste of Formulation Example 4 easily passes through the heating furnace without sticking to the support heated to 200°C in the heating furnace. We were able to obtain the above flooring material. This flooring material was tested for releasability and warping in the same manner as in Example 1, and as a result, it was confirmed that this flooring material had the basic performance necessary as a removable flooring material. The test results are in Table-5
Shown below. Example 5 The ethylene-vinyl acetate copolymer emulsion of Formulation Example 5 was coated on glass fiber paper with a coarse fiber structure of 0.22 m/m using a doctor knife coater so that the total thickness after drying was 0.4 m/m. coated and heated in a heating furnace
Heat and dry at 140°C for 5 minutes to form a heat-resistant synthetic resin layer, cool and then roll up. Then, 0.5% of the vinyl chloride resin paste of Blend Example 10 was applied to the surface opposite to the coated surface of the ethylene-vinyl acetate copolymer emulsion.
m/m thickness, heat solidified in a heating oven at 180°C for 1 minute, print in the same manner as in Example 1, and then apply 0.3% of the vinyl chloride resin paste of Formulation Example 12 on this surface. A flooring material was prepared under the same conditions as in Example 1 by applying the coating to a thickness of m/m. The above ethylene
Even when the heat-resistant synthetic resin layer formed from the vinyl acetate copolymer emulsion comes into contact with the support heated to 200°C in the heating furnace, it does not stick to it and easily passes through the heating furnace. I was able to get the flooring. This flooring material was tested for releasability and warping in the same manner as in Example 1, and as a result, it was confirmed that this flooring material had the basic performance required as a removable flooring material. The test results are in Table-5
Shown below. Examples 6 to 9 The self-crosslinking synthetic resin emulsions or self-crosslinking synthetic rubber latexes of Compounding Examples 6 to 9 were placed on coarse glass fiber paper with a fiber structure of 0.22 m/m, and the total thickness after drying was 0.4 m/m. A heat-resistant synthetic resin layer was formed under the same conditions as in Example 5 and wound up. Then, the vinyl chloride resin paste of Formulation Example 10 was applied to the surface opposite to the applied surface of the synthetic resin emulsion or synthetic rubber latex to a thickness of 0.5 m/m, and heated to a thickness of 180 m/m in a heating furnace.
After heating and solidifying at ℃ for 1 minute, printing was performed in the same manner as in Example 1, and then the vinyl chloride resin paste of Formulation Example 12 was applied to the surface at a thickness of 0.3 m/m, and the same as in Example 1 was applied. The flooring material was created under the following conditions. The heat-resistant synthetic resin layer formed from the above synthetic resin emulsion or synthetic rubber latex is
Even when it came into contact with a support heated to 200°C, it did not stick to the support and easily passed through the heating furnace, yielding the above-mentioned flooring material. Example 1 about this flooring material
As a result of testing for removability and the presence of warpage using the same method as above, it was confirmed that this flooring material had the basic performance required as a removable flooring material. The test results are shown in Table-5. Example 10 The self-crosslinking acrylic resin emulsion of Formulation Example 7 was coated on glass fiber paper with a coarse fiber structure of 0.3 m/m using a doctor knife coater so that the total thickness after drying was 0.4 m/m. A heat-resistant synthetic resin layer was formed under the same conditions as in Example 5 and wound up. Then, the vinyl chloride resin paste of Formulation Example 11 was applied to the surface opposite to the applied surface of the self-crosslinking acrylic resin emulsion at a thickness of 1.3 m/m, and the paste was heated and solidified at 180° C. for 1 minute in a heating furnace. After that, a predetermined pattern was printed on this surface using a gravure printing machine, and then the vinyl chloride resin paste of Formulation Example 13 was applied to a thickness of 0.30 m/m using a doctor knife coater, and heated at 200°C in a heating furnace. Heat and melt for 3 minutes, emboss with a specified aperture, and then irradiate with ultraviolet rays at a speed of 3 m/min at a distance of 15 cm using 3 high-pressure mercury lamps of 80 W/cm to coat the heat-resistant vinyl chloride resin. A layer was formed to obtain a flooring material with a total thickness of 2.0 m/m.
At this time, the heat-resistant synthetic resin layer formed from the self-crosslinking acrylic resin emulsion of Formulation Example 7 does not stick easily even when it comes into contact with the support heated to 200°C in the heating furnace. It passed through a heating furnace, and the above-mentioned flooring material could be obtained. This flooring material was tested for releasability and warping in the same manner as in Example 1, and as a result, it was confirmed that this flooring material had the basic performance necessary as a removable flooring material. In addition, as a result of conducting the following cigarette rubbing test and cigarette leaving test on this flooring material,
It was confirmed that it has excellent resistance to cigarette flames. <Tobacco fire resistance test method> Cigarette rubbing test Rub a lit cigarette on the surface of the flooring material, extinguish it,
Observe the flooring surface for discoloration and damage. Evaluation was performed according to the following criteria. 5th grade: No damage or discoloration on the flooring surface 4th grade: No damage to the flooring surface, discoloration to pale yellow 3rd grade: No damage to the flooring surface, partially discolored to black 2nd grade: Partial dents, overall black discoloration Grade 1 Severe burn damage, overall black discoloration Cigarette storage test A lit cigarette was left on the surface of the flooring material, and the time until scorch marks appeared on the flooring material was measured. The longer the time, the better the cigarette flame resistance. Comparative Examples 1 to 2 The vinyl chloride resin paste of Comparative Formulation Examples 1 to 2 was applied to a thickness of 0.20 m/m using a doctor knife coater on glass fiber paper with a dense fiber structure of 0.25 m/m, and then heated in a heating furnace. Heat and solidify at 200°C for 2 minutes to form a synthetic resin layer, cool and then roll up. Then, the vinyl chloride resin paste of Formulation Example 10 was applied to the surface opposite to the surface to which the vinyl chloride resin paste was applied at a thickness of 0.5 m/m using a doctor knife coater, and heated at 180°C for 1 minute in a heating furnace. After heating and solidifying, a predetermined pattern was printed on the surface using a gravure printing machine, and then the vinyl chloride resin paste of Formulation Example 12 was applied to a thickness of 0.30 m/m using a doctor knife coater, and then heated in a heating furnace. When heated at 200℃ for 3 minutes,
When the synthetic resin layer formed from the vinyl chloride resin paste of Comparative Formulation Example 1 comes into contact with the support heated to 200°C in the heating furnace, it sticks to the support, and the foamed material is foamed in the heating furnace. It was not possible to obtain the desired flooring material by cutting. Comparative Example 3 The ethylene-vinyl acetate copolymer emulsion of Comparative Formulation Example 3 was coated on glass fiber paper with a coarse fiber structure of 0.22 m/m using a doctor knife coater so that the total thickness after drying was 0.3 m/m. The resin layer is applied by heating and drying in a heating oven at 80°C for 10 minutes to form a synthetic resin layer, and after cooling, it is rolled up. Then, the vinyl chloride resin paste of Formulation Example 10 was applied to the surface opposite to the applied surface of the ethylene-vinyl acetate copolymer emulsion to a thickness of 0.55 m/m using a doctor knife coater, and heated to a thickness of 180 m/m in a heating furnace. When attempting to solidify by heating at ℃, the synthetic resin layer formed from the ethylene-vinyl acetate copolymer of Comparative Formulation Example 3 was heated to 180℃ in the heating furnace.
When it comes into contact with a support heated to ℃, it sticks to it,
It was not possible to obtain the desired flooring material by cutting it in the heating furnace. Comparative Example 4 The vinyl chloride resin paste of Formulation Example 10 was coated on 0.8 m/m asbestos paper with a thickness of 0.3 m/m using a doctor knife coater, and after solidifying by heating at 180°C for 1 minute in a heating furnace, After printing a predetermined pattern on this surface using a gravure printing machine, the vinyl chloride resin paste of Formulation Example 12 was applied to a thickness of 0.30 m/m using a doctor knife coater, and heated to 200°C in a heating furnace.
The material was heated for 3 minutes to create a flooring material. As a result of testing the removability of this flooring material in the same manner as in Example 1, it was found that a thick asbestos layer remained partially on the base.
The base was so uneven that it was impossible to construct a flooring material on top of it, and it could not be said to be a removable flooring material. Further, in order to compare the cigarette flame resistance of this flooring material with the flooring material prepared in Example 10, a test was conducted in the same manner as in Example 10, and as a result, it was confirmed that the cigarette flame resistance was poor.

【table】

[Table] (Effects) In the present invention, by coating and impregnating the fibrous base material 1 with a liquid synthetic resin composition, the fibrous base material 1 is integrated with the liquid synthetic resin composition, and further, the fibrous base material 1 is integrated with the liquid synthetic resin composition. The method of solidifying the liquid synthetic resin composition is by heating, ultraviolet irradiation, or electron beam irradiation, and since there is almost no internal distortion during processing, it is difficult to use the flooring material as described in Japanese Patent Publication No. 47-41848 in practical use. There are no problems such as deterioration of the dimensional stability of the flooring material due to interlayer peeling or internal strain during bonding of the soft plastic layer with a dense structure mixed with a large amount of filler. Furthermore, the present invention imparts heat resistance to the synthetic resin layer obtained by coating and impregnating a liquid synthetic resin composition on the fibrous base material 1 for the purpose of integrating the fibrous base material in order to make the flooring material easy to peel. By doing so, the synthetic resin layer is imparted with the heat resistance by heating when the soft synthetic resin intermediate layer 3 and the soft synthetic resin top layer 4 are sequentially laminated on the surface opposite to the surface on which the liquid synthetic resin composition is applied. The (heat-resistant synthetic resin layer) does not stick to the heated support in the heating furnace and can be easily laminated, simplifying the flooring manufacturing process. This has the advantage of improving productivity and providing flooring materials at low cost. Furthermore, as a liquid synthetic resin composition to be applied and impregnated onto the fibrous base material 1, it can be used as an adhesive for flooring construction to adhere to the base to the extent that no peeling occurs during practical use, and when the flooring material is to be peeled off. The thin layer of the heat-resistant synthetic resin layer 2 may peel off at the interface between the adhesive and the heat-resistant synthetic resin layer 2 obtained by solidifying the liquid synthetic resin composition, or the heat-resistant synthetic resin layer 2 may be destroyed. Since a material that peels off while remaining on the base together with the adhesive is used, there is no problem with the flooring material peeling off during practical use. In addition, the laminated flooring obtained by the method of the present invention does not leave any residue on the floor surface compared to conventional flooring made of asbestos sheets, and can be re-installed easily. This also has this effect.

[Brief explanation of the drawing]

The figure is an enlarged cross-sectional view of a flooring material obtained in one example of implementing the present invention. 1... Fibrous base material, 2... Heat resistant synthetic resin layer,
3... Soft synthetic resin intermediate layer, 4... Soft synthetic resin top layer, 5... Printing layer.

Claims (1)

[Claims] 1. A liquid heat-resistant synthetic resin composition was coated and impregnated on a fibrous base material to form an impregnated layer, and this impregnated layer was solidified to form a heat-resistant synthetic resin layer, and then this heat-resistant synthetic resin layer was formed. A method for manufacturing a laminated flooring material, comprising sequentially forming a soft synthetic resin intermediate layer and a soft synthetic resin top layer on the surface of a fibrous base material opposite to the surface to which a liquid synthetic resin composition is applied.